Compound for treating petroleums



Patented Mar. 3, 1936' UNITED STATES 2,032,527 COMPOUND FOR TREATING PETBOLEUMS James E. Cox, Oakland, Calif., assignor, by mesne assignments, .to D. M. Dorman, Los Angeles,

Calif.

No Drawing. Application October 29, 1934, Serial N0. 750,599

9 Claims. (01. 252-1) The invention, in general, relates to means for conditioning petroleums for refinery operations, as well as to refining operations, per se. More particularly, the'invention relates to a treating compound for quickly and efiiciently breaking water-in-oil or oil-in-water emulsions, and also for recovering increased quantities of the gasoline fraction from petroleums, including refinery residuums, upon straight-run distillation.

One of the principal objects of my invention is to provide an efiicient and inexpensively manufactured compound for dehydrating wet petroleums.

Another object of the invention is to provide a compound of the above mentioned character which is highly eflicaceous in dehydrating petroleums though used in but minute proportion to the quantity of the emulsion treated.

A further object of the invention is to provide a dehydrating agent for petroleums which is rapid and efiicient in performance.

A still further object of my invention is to provide a dehydrating means for petroleums of the character above specified, which functions efliciently and quickly even though the treated oil be maintained at ordinary room temperatures, although a slight warming of the mixture, together with agitation, enhances dehydration as reg ds the time element.

Another object of my invention is to provide a compound for treating dry petroleums and/or refinery residuums which affords increased yields of gasoline fractions therefrom upon subjecting the petroleums or residuums to but ordinary straight-run distillation.-

A still further object-of the invention is to provide a treating compound for use in the refining of petroleums and adapted to be recurrently applied to residuums or bottoms of distilled petroleums thereby to enable the production of gasoline fractions from the treated residuums or bottoms by normal straight-run distillations.

Other objects of the invention, together with some of the advantageous features thereof, will appear from the following description and specification. While a preferred mode of preparing my treating compound, as. well as the preferred compound itself, are hereinafter set forth, it is to be understood that I am not to be limited to the specific method ofpreparation described nor to the specified compound or compositions, inasmuch as the invention, as defined in the appended claims, can be embodied in a plurality and variety of forms and can be manufactured in a plurality and variety of ways. In other words, the specification sets forth merely preferred modes of preparation of the compound and preferred compositions per $8.

In its preferred form, the treating compound of my invention preerably comprises an admix- 5 .ing compound of my invention consists of a sludge derived from shale, and I preferably utilize a shale of the character found in a drift located in Palomares Canyon, near Hayward, Alameda County, State of California.

The shale sludge for the compound may beprepared in a number and variety of ways, and

either by employing a closed or a partially closed system, although I preferably used a closed sys-" tem for manufacturing the sludge. It may be added here that a closed system is preferred because it has been found expedient to utilize the gases generated by the shale to assist in further activation of the shale.

In order to prepare the sludge forming a part of my compound, a quantity of the above-mentioned shale is suspended in water, and preferably with water that has seeped through a deposit of shale of the character referred to. The suspended shale is allowed to set, while continually feeding or. passing the water through the same, until generation of gases has ceased. Preferably, the action is accelerated by intermixing calcium carbide with the water suspended shale, as well as by maintaining the temperature of the mixture around 98 F, While gases are being given off from the mixture, the sludge is being formed and is taken oif, preferably by means of air under pressure, to a separate container.

The gases from the mixture of shale suspend ed in water and calcium carbide are passed through a light petroleum distillate, such as kerosene or a light lubricating oil stock, in order that ingredients desirable in the compound and which are given ofi by the mixture, and carried away in part by the gases (also in part by the shale sludge) may be absorbed by the distillate. This combination of a distillate and absorbed ingredients from the mixture hereinabove mentioned may be termed, for convenience, the light j concentrate of the compoimd of my invention.

In accordance with the invention, the shale sludge, as above described, is mixed with an aqueous extract of tobacco cuttings (approximately 3% by weight of cuttings used to the total amount, by weight, of shale used), and is then filtered, the filtrate constituting what may ,be conveniently termed the heavy concentrate of the extract. The ratio of sludge to extract oftobacco may be varied to some extent without departing from the scope of the invention, as it is reasonable and I have found that. different emulsions as well as dry oils. require different compositions of the'same compound in order to obtain the most eilicient and substantially uniform results. The heavy concentrate itself is a reasonably good dehydrator for wet petroleums.

In addition to the light and heavy concentrates hereinabove described, the compound of my invention includes means for forming thereof a diflicult-toz-disintegrate pseudo emulsion or a moderately stable emulsion. The soap functions also to prevent the adherence of the compound, as well as mixtures of the compound and petroleums, to the walls of containers or pipes. Preferably, sodium oleate is used as the soap of the compound, although any other suitable soap,

such as sodium stearate or sodium palmitate may be employed, as desired. The latter twosoaps, however, require excessive quantities of a solvent as well as the two concentrates, in excess, to prepare an flicaceous compound or solution. To dissolve the sodium oleate and hence prepare it for intermixture with the two concentrates, I preferably utilize either an acid, such as cresylic acid, or an oil, suh as c'resol or substances known commercially as castor oil and "castor machine oil. Approximately two to two and one-half parts by volume of the solvent are used to one part by weight of the sodium oleate. The latter substance can be commercial sodium oleate but can be made, of course, by mixing a 50% sodium hydroxide solution with oleic acid.

For both treating a dry petroleum or a refinery residuum to provide an increase in gasoline fraction derivable therefrom, as well as breaking a water-in-oil emulsion, I have found that admixtures of the foregoing named and described substances in the approximate proportions given in the following examples, will give excellent results, the formula varying somewhat depending upon' the oil treated and in accordance with the water content thereof, the viscosity of the crude, and the impurities therein:

Example '1 r v Per cent Heavy concentrate 27 Light concentrate -a 27 Soap (preferably sodium oleate) 2'7 Solvent (preferably cresylic acid) 19 Example 2 Heavy concentrate 15 Light concentrate I 30 Soap 15 Solv 40' Example 3 Per cent Heavy concentrate 10 Light concentrate 20 Soap 25 Solvent 45 The more diflicult-to break emulsions are treated withtheformula of Example 1, supra, while the less dlflicult-to-break emulsions are treated with the formula of Examples 2 and 3. In other words, the formula containing the greater percentage of concentrates is employed for the more diflicult-to-break emulsions, while a weaker solution, that is, containing lesser percentage of the concentrates is used for the more moderate orless difficult-to-break emulions. I have found that approximately one part by volume of my compound to approximately two hundred and fifty parts by volume of the waterin-oil or oil-in-water emulsion will give eflicient results at ordinary room temperatures. The efficiency of dehydration as regards time or rate of dehydration is aided if the mixture of com-' pound and oil is moderately heated and the whole is subjected to agitation, which may consist of a steady, oscillatory movement..

As hereinabove stated, the compound of my invention is especially suitable for treating dry petroleums and/or refinery residuums in order and repeated. Either one of the formula of.

Examples 1 to 3 inclusive, given above, may be applied to a petroleum or a refinery residuum for raising the gasoline fraction yield therefrom, although I have found that with extremely heavy, low A. P. I.'gravity crudes and refinery residuums the-formula of Example 1, containing the greater quantity of concentrates is more suitable than the other formula given. For relatively light crudes of higher A. P. I. gravity, the formula of Examples 2 and 3 can be efficiently used. I have also found that the proportion of compound to oil treated varies somewhat in accordance with the character thereof, 'some'oils requiring but one part by volume of the compound to approximately two hundred to two hundred and fifty. parts by volume of the oil, while with respect to other oils, it requires one part by volume of the compound to approximately one hundred parts by volume of the crude. I

have further found that once the proportion of compound to quantity of an oil treated is established, resulting in an increase in the yield of gasoline fraction derivable from such treated 011, an increase in-the amount of compound added to the oil will not materially affect the yield of the gasoline fraction.

While I have been able to obtain increases in the yield of gasoline fraction upon straight-run distillation of a petroleum or a refinery residuum treated-with the compound of my invention at ordinary room temperatures and with but Blight. agitation, I have found that still greater yields of gasoline fraction can be obtained from petroleums and refinery residuums treated with my compound if the mixtures are subjected to great agitation and the temperature of the mixture during agitation is maintained approximately between F and 220 F., the agitation and application of heat preferably being applied for approximately twenty to thirty minutes. Preferably, the last mentioned mode of treatment is carried out in a closed system.

Although it ispossible to use the compound of my invention practically immediately after it has been prepared, I preferably allow the composition vto set for a period of from twenty-four to forty-eight hours. This conditioning of the compound not only accelerates the rate of dehydration of a water-in-oil or an oil-in-water emulsion containing the "conditioned compound, but also materially affects the amount, that is favorably, of the gasoline fraction obtainable from a treated crude. However, I have found it advantageous to allow a mixture of my conditioned" compound and a dry petroleum or refinery residuum to set for an appreciable period of time before distilling the same. In other words, the important point in treating either water-in-oil emulsions for dehydration, or in treating adry crude or residuum for increasing the gasoline fraction content thereof is .the intimate contact of the compound of my invention with the treated oil.

It is to be understood that the appended claims are to be accorded a range of equivalents commensurate with the scope of the prior art.

I claim:

1. A composition for treating petroleums for dehydration of the .same and for raising the gasoline fraction content thereof; said composition comprising "a filtrate of a mixture ofa shale sludge and extract of tobacc -a petroleum distillate containing absorbed ingredients of said sludge, and an emulsifying agent for said filtrate and said distillate; said agent comprising a soap, and a solvent for said soap. 2. A compound, for treating petroleums and adapted to break water-in-oil emulsions as well as to increase the gasoline fraction content of a 1 dry petroleum or a refinery residuum; said compound comprising a flltrate of a mixture of a shale sludge and extract of tobacco, and an emulsifying agent for said. filtrate: said agent comprising a soap, and a solvent for said soap.

3. A composition for treating petroleums and adapted to dehydrate the same as well as to increase the gasoline fraction content thereof; said composition comprising a filtrate of a mixture of a shale sludge and an aqueous extract of tobacco, a petroleum distillate containing absorbed ingredients of said shale sludge, and an emulsifying agent for said filtrate and said distillate'; said agent comprising sodium oleate, and cresylic acid.

4. A compound for treating petroleums and adapted to dehydrate the same as well as to increase the gasoline fraction content thereof; said compound comprising the residue and the tops of a distillate of a mixture of a shale sludge and an aqueous extract of tobacco, and an emulsifying agent for said residue and tops; said agent comprising a soap, and a light lubricating 011 stock.

5. A dehydrator for water-in-oil emulsions, said dehydrator comprising a filtrate of a mixture of a shale slucke and extract of tobacco.

6. A dehydrator for water-in-oil emulsions, said dehydrator comprising a filtrate of a mixture of a shale sludge and extract of tobacco, a soap, and a solvent for said soap.

7. In a composition for treating petroleums, the residue and topsof a distillate of a mixture of a shale sludge and an aqueous extract of tobacco.

8. In a compound for treating petroleums and adapted to dehydrate the same as well as to increase the gasoline fraction content thereof,

an emulsifying agent for a shale sludge and extract of tobacco; said agent comprising a soap, characterized by sodium oleate,and a solvent for said soap, characterized by a light lubricating oil.

I 9. A composition for treating petroleums comprisirm a filtrate of a mixture of shale sludge and an aqueous extract of tobacco, a petroleum distillate containing absorbed ingredients from said sludge, and an emulsifying agent for said JAB/IE3 E. COX. 

